Process for the preparation of emulsions



United States Patent masses rnocnss non rrm rrA'rroN or nMULsroNs CarlBoresch and Mathieu Quaedvlieg, Leverlrusen, and Walter Wonder, Cologne-Flittard, Germany, assignors to Farheniabriiren BayerAktiengesellschatt, Leverkusen, Germany, a German corporation NoDrawing. Filed Nov. 14, 1%1, er. No. 152,148 filairns priority,application Germany, Nov. 16, 196%, F 32,564; Nov. 3, H61, F 35,313 4Qlaims. (Cl. 106-271) and to the compounds of the type B in the firstplace compounds of the general formula In these formulae denote R:hydrogen or a hydrocarbon radical R1: hydrogen or a hydrocarbon radicalR2: hydrogen or a hydrocarbon radical R hydrogen, a hydrocarbon radicalor one of the groups RCH:O and As representatives of compounds of thetype A there may be mentioned for example saturated and unsaturatedhigher fatty acids, montanic acid esters containing free carboxylicgroups as well as N-acyl-sarcosien. As representatives of compounds ofthe type B there may be mentioned for example iormamide, dimethylformamide, acetamide, dimethyl acetarnide, carbamic acid methyl ester aswell as urea.

Depending on the circumstances, the dissolving of the compounds or" thetype A or the type B in the substances to be emulsified or in thehomogeneous phase can also be carried out with the aid of a solubilizer,such as ethanol, isopropanoyl, benzene or tetrahydronaphthalene.

The process according to the invention enables substances of varioustypes, for example aliphatic and aromatic hydrocarbons such as solidparafiins, chlorinated paraiiins, benzines, mineral oils, benzene,chlorinated benzene, toluene and xylene, furthermore waxes and fats suchas saturated and unsaturated triglycerides, and also silicones, to beexcellently emulsified in, 'for example, water.

The proportion of compounds A and B to the substances to be emulsifiedmay vary within wide limits, it is, however, advisable to use at leastone mol of the compound B per mol of the compound A.

Conventional mechanical devices can be used for the preparation of theemulsions; it is advantageous to employ a turbo mixer;

The emulsions obtained according to the process of the invention possessvaluable properties. If the homogeneous phases permits a dissociation,the emulsions are weakly acidic. When water is used as the homogeneousphase the emulsions can be diluted.

It is further noteworthy that the emulsions are saltt'ree and do notshow hydrophilic properties when applied to substrates after drying.Hitherto known emulsions do not possess these characteristics or not tothe same extent. The emulsions of the present invention can be appliedin many Ways. They can be used in all cases where the correspondingemulsions obtainable by hitherto known processes are employed. Onaccount of their neutral or weekly acid reaction they are, forexample,especially suitable for cosmetic preparations.

When the process of the present invention is used for the preparation ofaqueous emulsions of parafiins, waxes or silicon-es which are to beapplied for hydrophobing fibrous materials, such as textile materials,leather or paper, it is advantageous to add Zirconium salts, forinstance zirconium oxychloride or acid zirconium acetate, to theemulsions at any stage of their preparation. The emulsions thus obtainedexhibit a hydrophobing action which is superior to the hydrophobingaction of the aqueous emulsions of parafiins, waxes or siliconeshitherto prepare with the addition of zirconium salts.

The aqueous emulsions prepared according to the invention are stableeven if zirconium salts are added.

rThis is surprising, for the emulsions of the invention which belong tothe anionic type are sensitive towards acids, and the zirconium saltsshow a strongly acid reaction in aqueous solution.

Suitable proportions of the components to be applied in the perrormanceof the present invention can easily be determined by preliminary tests.Some indications are given in the following examples which serve toillusstrate the invention without, however, limiting the scope thereof;the parts indicated are parts by weight.

Example 1 30 parts of montanic acid (acid number 140, saponificationnumber 165, MP. about C.) are dissolved at C. in 80 parts of liquidparaffin DAB VI. The resultant hot solution is introduced whilevigorously stirring (8600 rpm.) into a solution of 6 parts of urea in440 parts of water at 8590 C. The emulsion formed is further vigorouslystirred for some time and then cooled while stirring.

Instead of 6 parts of urea there may also be used 5 parts of formamide,9 parts of dimethyl formamide, 7 parts of acetamide or 10 parts of acarbamic acid methyl ester.

Example 3 30 parts of montanic acid (acid number 140, saponificationnumber 1 65, MP. about 80 C.) are dissolved at 85 C. in 100 parts ofparaflln ('M.P.'5-25'4 C.). The resultant hot solution is introducedwhile vigorously stirring 8000 rpm.) into .a solution of 4.5 parts ofurea in 400 parts of water at 85-90 C. The emulsion formed is furthervigorously stirred for some time and then cooled with stirring. Example4 30 parts of montanic acid (acid number 140, saponittication number165, MJP, about 80 C.) are dissolved at 85 C. in 80 parts of siliconeoil.

The resultant hot solution is introduced while vigorously stirring (8000rpm.) into .a solution of 7 parts of :acetamide in 440 parts of water at85-90 C. The emulsion formed is further vigorously stirred for some timeand then cooled with stirring.

Example 5 16 parts of first runnings of coconut oil fatty acid (acidnumber 354) are dissolved at 85 C. in 80 parts of liquid parafiin DABVI. The resultant hot solution is cooled and mixed with 4 parts ofsaturated aqueous sodium acetate solution.

Example 9 parts of mo-ntanic acid (acid number 140, saponificationnumber 165, M.P. about 80 C.) are dissolved at 85 C. in 120 parts ofpa-rafiin (M:P. 52-54 C.). The resultant hot solution is introducedwhile vigorously stirring (8000 r.p.m.) intoa solution of 9parts of ureain 600 parts of Water at 8590 C. The emulsion formed is furthervigorously stirred for 20 -minutes and then cooled with stirring to 30C. Thereupon 180 parts of an aqueous solution of zirconyl acetatecontaining 8.5 percent by weight of Zr0 are introduced into the emulsionat 30 C.

I Example 10 49 parts of montanic acid (acid number 140, saponificationnumber 165, MP. about 80 C.) are dissolved at 85 C. in 9.7' parts ofparaflin (M.P. 5254 C.). The resultant hot solution is introduced whilevigorously stirring (8000 11pm.) into a solution of 9 parts of urea in600 parts of water at 85-90 C. The emulsion formed is further vigorouslystirred for .20 minutes and then cooled with stirring to 30 C. Thereupon180 parts of an aqueous solution'of zirconyl acetate containing 8.5percent by weight of Zr0 are introduced into the emulsion at 30C. i

' Example 11 V 4.9 parts of montanic acid (acid number 140,saponification number 165, MP. about 80 C.) are dissolved at 85. C. in9.7 parts of parafiin (M:P. 52-54 C.). The

introduced while vigorously stirring (8000 r.p.rn.) into a solution of14 parts of urea in 440 parts of water at 8590 C.' The emulsion formedis further vigorously stirred for some time and then cooled withstirring.

Example 6 29 par-ts of linseed oil fatty acid (acid number 194) aredissolved at 85 C. in 80 parts of olive oil. The resultant hot solutionis introduced while vigorously stirring (8000 r.p.m.) into a solution of8 parts of urea in 440 parts of water .at 8590 C. The emulsion for-medis further vigorously stirred for some time and then stirred withcooling.

Example 7 7.3 parts or montanic acid (acid number 140, sapon-itfica tionnumber 165, M.P. about 80 C.) are dissolved at 85 C. in 14.6 partsofparafiin (M.P. 52-54 C.). The resultant hot solution is introducedwhile vigorously stirring (8000 rpm.) into a solution of 2.8 parts ofurea in 43 parts of water at 85-90 C. The emulsion formed is furthervigorously stirred until the size of the particles of theparatfin-montanic-acimmixture in the emulsion is below 2;. Thereupon theemulsion is introduced While continuously stirring at 95 C. into asolution prepared from 7.3 parts of zirconium oxychloride (Z-rOCl -8H O)and 18.3 parts of water warmed to 85 C. The stirring is continued untilthe size of the particles of the parafiinmontanic-acid n-ixture in theemulsion which first increases on account of the addition of thezirconium salt again decreases to below 2 Finally the emulsion isresultant hot solution is introduced while vigorously stirring (8000rpm.) into a solution of 1.8 parts urea in 55.1 parts of water at -90 CIThe emulsion formed is further vigorously stirred and then mixed with asolution prepared from 5.3 parts of zirconium oxychloride (ZrOCl -8H O),15.8 parts of water and 4 parts of saturated aqueous sodium acetatesolution. Finally the emulsion is homogenized.

Example 12 12 parts of montanic acid (acid number 140, saponificationnumber 165, MJP. about 80C.) are dissolved at room temperature in asolution prepared from 48 parts of hydrogenpolysiloxane, 18 parts ofisopropanol and 18 parts of tetrahydronaphthalene. The ,clear solutionobtained is introduced while vigorously stirring (8000 rpm.) into asolution of 4.5 parts of urea in 200 parts of Water. Thereupon theemulsion is mixed while stirring with 140 parts of a solution preparedfrom 53 parts of zirconium oxychloride (ZrOCl -8H O), 158 parts of Waterand 74 parts of saturated aqueous sodium acetate solution. The emulsionsprepared according to the Examples 8-1-2 can be used for hydrophobingtextile materials for instance in the following manner:

The materials are impregnated in an aqueous bath containing per litre50-80 g. of the emulsions, then squeezed to an increase of weight ofabout 6080 percent and heated to C. for 2-4 minutes. Fabricsmanufactured from fibres of polymeric e-caprol actam or fabrics frompoly-ester fibres and cotton thus treated show a water absorption of 58percent after spraying for 10 minutes in the Bundesmann apparatus. ifthe emulsions are to be applied to fabrics of, cotton, it is advisableto add 10 g. of the methylether of trirnethylolmelamine per litre of theimpregnation bath; the fabrics show then, a water absorption of 12%. Theresistance to water pressure determined according to the Scho-ppermethod amounts to a pressure of. 500 mm. water.

We claim:

'1. As a new composition of matter, an emulsion prepared by dissolving acompound A in the substance to be emulsified and a compound B in thesubstance which will form the homogeneous phase of the emulsion andsubsequently forming a dispersion from the aforesaid materials, compoundA being a member selected from the group consisting of saturated andunsaturated higher fatty acids, montanic acid esters containing freecarboxyl groups, and N-acyl sarcosine, and compound B being a memberselected from the group consisting of formamide, dimethyi forrn amide,acetamid-e, dimethyl acetamide, methyl carbam'ate and urea, compounds Aand B having the ability to form adducts at the boundary surface of thedispersed phase of the resultant emulsion and being present in a ratioof at least one mol of B per mol of A.

2. The emulsion of claim 1 containing a zirconium salt.

3. The emulsion of claim 1 wherein the substance to be emulsified isselected from the group consisting of solid parafiins, chlorinatedparaflins, benzines, mineral oils, benzene, chlorinated benzene,toluene, Xylene, waxes, fats and sil-icones.

4. The emulsion of claim 1 wherein the homogenous phase is water.

References Cited by the Examiner UNITED STATES PATENTS 1,643,675 9/27Montgomerie 252311.5 1,'952,0()8 3/34 Bruson 2'357 XR 2,302,697 1 1/ 42Katz-man 252-357 2,304,125 12/42 Shutt et al. 252-495 2,457, 853 6/49Mater 106--243 2,737,458 3/56 Burnham 106-471 2,7 59,851: 8/56 Pluck etal.

2,769,724 11/56 Studenic et al. 117-55 2,838,422 6/58 Orthner et al.10=6243 OTHER REFERENCES Chemical Behavior of Zirconium, Blumenth-al,1958, 'D. Van Nostrand Co. Inc., N.Y., page 318.

ALEXANDER H. BRODIME-RKEL, Primary Examiner.

JOSEPH REBOLD, MORRIS LIEBMAN, Examiners.

1. AS A NEW COMPOSITION OF MATTER, AN EMULSION PREPARED BY DISSOLVING ACOMPOUND A IN THE SUBSTANCE TO BE EMULSIFIED AND A COMPOUND B IN THESUBSTANCE WHICH WILL FORM THE HOMOGENEOUS PHASE OF THE EMULSION ANDSUBSEQUENTLY FORMING A DISPERSION FROM THE AFORESAID MATERIALS, COMPOUNDA BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF SATURATED ANDUNSATURATED HIGHER FATTY ACIDS, MONTANIC ACID ESTERS CONTAINING FREECARBOXYL GROUPS, AND N-ACYL-SARCOSINE, AND COMPOUND B BEING A MEMBERSELECTED FROM THE GROUP CONSISTING OF FORMANMIDE, DIMETHYL FORMAMIDE,ACETAMIDE, DIMETHYL ACETAMIDE, METHYL CARBAMATE AND UREA, COMPOUNDS AAND B HAVING THE ABILITY TO FROM ADDUCTS AT THE BOUNDARY SURFACE OF THEDISPERSED PHASE OF THE RESULTANT EMULSION AND BEING PRESENT IN A RATIOOF AT LEAST ONE MOL OF B PER MOL OF A.